Separator and electrochemical device containing the same

ABSTRACT

A separator and an electrochemical device including the same. The separator includes an adhesive layer including first adhesive resin particles having an average particle diameter corresponding to 0.8-3 times of an average particle diameter of the inorganic particles and second adhesive resin particles having an average particle diameter corresponding to 0.2-0.6 times of the average particle diameter of the inorganic particles, wherein the first adhesive resin particles are present in an amount of 30-90 wt % based on a total weight of the first adhesive resin particles and the second adhesive resin particles. The separator shows improved adhesion to an electrode and provides an electrochemical device with decreased increment in resistance after lamination with an electrode.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a By-Pass Continuation of InternationalApplication PCT/KR2018/015724, filed Dec. 11, 2018, which claimspriority to Korean Patent Application No. 10-2017-0169386, filed on Dec.11, 2017, in the Korean Intellectual Property Office, the disclosures ofwhich are incorporated herein in their entirety by reference.

TECHNICAL FIELD

The present disclosure relates to a separator that may be used for anelectrochemical device, such as a lithium secondary battery, and anelectrochemical device including the same.

BACKGROUND ART

Recently, energy storage technology has been given increased attention.Efforts into research and development for electrochemical devices havebeen actualized more and more, as the application of energy storagetechnology has been extended to energy for cellular phones, camcorders,notebook PC and electric vehicles. In this context, electrochemicaldevices have been spotlighted. Among such electrochemical devices,development of rechargeable secondary batteries has been of focus. Morerecently, active studies have been conducted about designing a novelelectrode and battery in order to improve the capacity density andspecific energy in developing such batteries.

Among commercially available secondary batteries, lithium secondarybatteries developed in the early 1990's have been spotlighted, sincethey have a higher operating voltage and significantly higher energydensity as compared to conventional batteries, such as Ni—MH, Ni—Cd andsulfuric acid-lead batteries using an aqueous electrolyte.

Although such electrochemical devices have been produced from manyproduction companies, the safety characteristics thereof show differentsigns. Evaluation and securement of the safety of such electrochemicaldevices are very important. The most important consideration is thatelectrochemical devices should not damage users upon their malfunction.For this purpose, safety standards strictly control ignition and smokeemission in electrochemical devices. With regard to safetycharacteristics of electrochemical devices, there is great concern aboutexplosion when an electrochemical device is overheated to cause thermalrunaway or perforation of a separator. Particularly, a polyolefin-basedporous substrate used conventionally as a separator for anelectrochemical device shows a severe heat shrinking behavior at atemperature of 100° C. or higher due to its material property and acharacteristic during its manufacturing process, including orientation,thereby causing a short-circuit between a cathode and an anode.

To solve the above-mentioned safety problem of an electrochemicaldevice, there has been suggested a separator having a porousorganic/inorganic coating layer formed by coating a mixture of anexcessive amount of inorganic particles with a binder polymer onto atleast one surface of a porous polymer substrate having pores. Inaddition, an adhesive layer has been introduced onto the porousorganic/inorganic coating layer in order to increase the adhesionbetween a separator and an electrode.

However, the adhesive layer according to the related art merely usesadhesive resin particles having a uniform diameter, and thus theadhesive resin particles are accumulated homogeneously in the adhesivelayer to cause high resistance of the separator. On the other hand, whenreducing the coating amount of adhesive resin particles to reduceresistance, the adhesion between a separator and an electrode isdecreased undesirably.

DISCLOSURE Technical Problem

The present disclosure is directed to providing a separator which mayhave improved adhesion to an electrode and may show decreased incrementin resistance after lamination with an electrode.

The present disclosure is also directed to providing an electrochemicaldevice including the separator.

Technical Solution

In one aspect of the present disclosure, there is provided a separatorfor an electrochemical device according to any one of the followingembodiments.

According to an embodiment, there is provided a separator for anelectrochemical device which includes:

a porous polymer substrate having pores;

a porous coating layer present on at least one surface of the porouspolymer substrate, and including inorganic particles and a binderpolymer disposed partially or totally on a surface of the inorganicparticles, wherein the binder polymer connects and fixes the inorganicparticles with each other; and

an adhesive layer present on a surface of the porous coating layer, andincluding first adhesive resin particles having an average particlediameter corresponding to 0.8-3 times of an average particle diameter ofthe inorganic particles and second adhesive resin particles having anaverage particle diameter corresponding to 0.2-0.6 times of the averageparticle diameter of the inorganic particles, wherein the first adhesiveresin particles are present in an amount of 30-90 wt % based on a totalweight of the first adhesive resin particles and the second adhesiveresin particles.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in the above embodiment, wherein theaverage particle diameter of the inorganic particles is 100-700 nm.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein the first and second adhesive resin particles independentlyinclude one or more selected from the group consisting of styrenebutadiene rubber (SBR), acrylonitrile-butadiene rubber,acrylonitrile-butadiene-styrene rubber, polybutyl acrylate-co-ethylhexylacrylate, polymethyl methacrylate-co-ethylhexyl acrylate,polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride,polyvinyl alcohol, styrene and polycyanoacrylate.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein the average particle diameter of the first adhesive resinparticles is 1-2.5 times of the average particle diameter of theinorganic particles, and the average particle diameter of the secondadhesive resin particles is 0.3-0.6 times of the average particlediameter of the inorganic particles.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein the average particle diameter of the first adhesive resinparticles is 1-2 times of the average particle diameter of the inorganicparticles, and the average particle diameter of the second adhesiveresin particles is 0.3-0.6 times of the average particle diameter of theinorganic particles.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein the first adhesive resin particles are present in an amount of50-85 wt % based on the total weight of the first adhesive resinparticles and the second adhesive resin particles.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein the inorganic particle include one or more selected from thegroup consisting of BaTiO₃, Pb(Zr_(x)Ti_(1-x))O₃ (PZT, 0<x<1),Pb_(1-x)La_(x)Zr_(1-y)Ti_(y)O₃ (PLZT, 0<x<1, 0<y<1),(1-x)Pb(Mg_(1/3)Nb_(2/3))O₃-xPbTiO₃ (PMNPT, 0<x<1), hafnia (HfO₂),SrTiO₃, SnO₂, CeO₂, MgO, NiO, CaO, ZnO, ZrO₂, Y₂O₃, Al₂O₃, AlO(OH),SiO₂, TiO₂ and SiC. According to another embodiment, there is providedthe separator for an electrochemical device as defined in any one of theabove embodiments, wherein the porous coating layer has a thickness of1-10 μm.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein the adhesive layer has a thickness of 0.5-3 μm.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein the porous coating layer is present directly on the surface ofthe porous polymer substrate.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein the adhesive layer is present directly on the surface of theporous coating layer.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein the first and second adhesive resin particles include the sameresin.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein the first and second adhesive resin particles include differentresins.

According to another embodiment, there is provided the separator for anelectrochemical device as defined in any one of the above embodiments,wherein an upper portion of the adhesive layer has a larger number ofpores as compared to a lower portion of the adhesive layer, said lowerportion being in contact with the surface of the porous coating layer.In another aspect of the present disclosure, there is provided anelectrochemical device according to any one of the followingembodiments.

According to another embodiment, there is provided an electrochemicaldevice including a cathode, an anode and a separator interposed betweenthe cathode and the anode, wherein the separator is as defined in anyone of the above embodiments.

According to another embodiment, there is provided the electrochemicaldevice as defined in the above embodiment, which is a lithium secondarybattery.

Advantageous Effects

In the separator according to an embodiment of the present disclosure,the adhesive layer is present (e.g., present by coating) on the surfaceof the porous coating layer and includes first and second adhesive resinparticles having a different ratio of average particle diameter based onthe average particle diameter of the inorganic particles. Thus, anincrement in resistance is relatively low after lamination of theseparator with an electrode. In addition, pores may be formed in theadhesive layer to cause a decrease in resistance. Further, the adhesionbetween the separator and an electrode may be improved significantly.

DESCRIPTION OF DRAWING

The FIGURE is a schematic view illustrating the separator according toan embodiment of the present disclosure.

BEST MODE

It should be understood that the terms used in the specification and theappended claims should not be construed as limited to general anddictionary meanings, but interpreted based on the meanings and conceptscorresponding to technical aspects of the present disclosure on thebasis of the principle that the inventor is allowed to define termsappropriately for the best explanation.

As used herein, the expression ‘one portion is connected to anotherportion’ covers not only ‘a portion is directly connected to anotherportion’ but also ‘one portion is connected electrically to anotherportion’ by way of the other element interposed between them.

Throughout the specification, the expression ‘a part ┌includes┘ anelement’ does not preclude the presence of any additional elements butmeans that the part may further include the other elements.

In addition, it will be understood that the terms “comprises” and/or“comprising”, or “includes” and/or “including” when used in thisspecification, refer to the presence of any stated shapes, numbers,steps, operations, members, elements and/or groups thereof, but do notpreclude the addition of one or more other shapes, numbers, steps,operations, members, elements and/or groups thereof.

As used herein, the terms ‘approximately’, ‘substantially’, or the like,are used as meaning contiguous from or to the stated numerical value,when an acceptable preparation and material error unique to the statedmeaning is suggested, and are used for the purpose of preventing anunconscientious invader from unduly using the stated disclosureincluding an accurate or absolute numerical value provided to helpunderstanding of the present disclosure.

As used herein, the term ‘combination(s) thereof’ included in anyMarkush-type expression means a combination or mixture of one or moreelements selected from the group of elements disclosed in theMarkush-type expression, and refers to the presence of one or moreelements selected from the group.

As used herein, the expression ‘A and/or B’ means ‘A, B or both ofthem’.

In an electrochemical device, such as a lithium secondary battery, anadhesive layer has been introduced onto a porous organic/inorganiccoating layer in order to increase the adhesion between a separator andan electrode.

However, since a conventional adhesive layer merely uses adhesive resinparticles having a uniform size, there is a problem of a rapid increasein resistance of an electrode assembly after lamination with anelectrode. On the other hand, when the coating amount of adhesive layeris decreased in order to reduce resistance, the adhesion between anelectrode and a separator is decreased undesirably.

To solve the above-mentioned problem, the separator for anelectrochemical device according to an embodiment of the presentdisclosure includes: a porous polymer substrate having pores; a porouscoating layer present on at least one surface of the porous polymersubstrate, and including inorganic particles and a binder polymerdisposed partially or totally on a surface of the inorganic particles,wherein the binder polymer connects and fixes the inorganic particleswith each other; and an adhesive layer present on a surface of theporous coating layer, and including first adhesive resin particleshaving an average particle diameter corresponding to 0.8-3 times of anaverage particle diameter of the inorganic particles and second adhesiveresin particles having an average particle diameter corresponding to0.2-0.6 times of the average particle diameter of the inorganicparticles.

As shown in the FIGURE, the separator 100 for an electrochemical deviceaccording to the present disclosure includes: a porous polymer substrate10; a porous coating layer 20 present on at least one surface of theporous polymer substrate; and an adhesive layer 30 present on a surfaceof the porous coating layer. The porous coating layer 20 includesinorganic particles 21 and a binder polymer (not shown). The adhesivelayer 30 includes first adhesive resin particles 31 having an averageparticle diameter corresponding to 0.8-3 times of an average particlediameter of the inorganic particles 21 and second adhesive resinparticles 32 having an average particle diameter corresponding to0.2-0.6 times of the average particle diameter of the inorganicparticles 21.

As used herein, the term ‘diameter’ or ‘average particle diameter’refers to the average particle diameter (D₅₀) of inorganic particles oradhesive resin particles, and may be defined as particle diametercorresponding to 50% of particle diameter distribution. According to anembodiment of the present disclosure, the average particle diameter maybe determined by using a laser diffraction method. The laser diffractionmethod can determine a particle diameter ranging from the submicronregion to several nm and provide results with high reproducibility andhigh resolution.

The separator according to an embodiment of the present disclosureincludes at least two types of adhesive resin particles having adifferent size (e.g., different average particle diameters) in theadhesive layer. When using adhesive resin particles having a uniformsize alone, the adhesive layer coated on the porous coating layer has astructure in which the adhesive resin particles are accumulatedhomogeneously, and thus shows high resistance. On the contrary, theadhesive layer according to the present disclosure includes adhesiveresin particles having a different size (e.g., at least first and secondadhesive resin particles) and the adhesive resin particles may beaccumulated loosely and/or coarsely in the adhesive layer, and thus theadhesive layer may show decreased resistance as compared to theconventional adhesive layer.

In addition, the separator according to an embodiment of the presentdisclosure may be advantageous in that Lami Strength may be increased ascompared to the adhesive layer merely including adhesive resin particleshaving an average particle diameter significantly smaller than theaverage particle diameter of the inorganic particles.

The separator according to an embodiment of the present disclosureincludes at least two types of adhesive resin particles having adifferent size (e.g., at least first and second adhesive resinparticles) in the adhesive layer, and may show significantly decreasedincrement in resistance after lamination with an electrode, as comparedto the adhesive layer merely including adhesive resin particles having auniform size.

The resistance after lamination with an electrode may be more affectedby the pore distribution and pore size in the area between the porouscoating layer and the electrode than the pore distribution and pore sizeof the porous coating layer. In other words, the resistance afterlamination may be more affected by the pore distribution and pore sizein the adhesive layer. The separator according to an embodiment of thepresent disclosure includes at least two types of adhesive resinparticles having a different average particle diameter (i.e., at leastfirst and second adhesive resin particles), wherein the second adhesiveresin particles having an average particle diameter corresponding to0.2-0.6 times of the average particle diameter of the inorganicparticles may be positioned closer to the surface of the porous coatinglayer as compared to an upper surface of the adhesive layer (said uppersurface being the surface to be contacted with the electrode). Forinstance, the second adhesive resin particles may be positioned in gapsin the inorganic particles forming the porous coating layer. Further,the first adhesive resin particles having a larger diameter as comparedto the inorganic particles may be positioned largely on the uppersurface of the porous coating layer. Therefore, as shown in the FIGURE,the portion of the adhesive layer where the adhesive layer will be incontact with the electrode, i.e., the upper surface of the adhesivelayer, has a larger number of pores as compared to the portion of theadhesive layer in contact with the porous coating layer, and thus showsdecreased increment in resistance after lamination with the electrode,as compared to the case in which conventional adhesive resin particleshaving a uniform size are used alone.

As shown in the FIGURE, the second adhesive resin particles in theseparator according to an embodiment of the present disclosure have anaverage particle diameter corresponding to 0.2-0.6 times of the averageparticle diameter of the inorganic particles. In other words, the secondadhesive resin particles have a smaller average particle diameter ascompared to the inorganic particles. Therefore, the second adhesiveresin particles may infiltrate the surface of the porous coating layerand a part of the porous coating layer to improve the adhesion of theinorganic particles among themselves and to improve the adhesion betweenthe inorganic particles and the first adhesive resin particles.

The separator according to an embodiment of the present disclosure isprovided with an adhesive layer including first adhesive resin particleshaving an average particle diameter corresponding to 0.8-3 times of theaverage particle diameter of the inorganic particles and the secondadhesive resin particles having an average particle diametercorresponding to 0.2-0.6 times of the average particle diameter of theinorganic particles. Preferably, the average particle diameter of thefirst adhesive resin particles is 1-2.5 times, and more preferably is1-2 times the average particle diameter of the inorganic particles is.In addition, the average particle diameter of the second adhesive resinparticles is 0.2-0.6 times, and more preferably is 0.3-0.6 times theaverage particle diameter of the inorganic particles.

When an adhesive layer includes at least two types of adhesive resinparticles having a different size, use of first adhesive resin particleshaving an average particle diameter larger than 3 times of the averageparticle diameter of the inorganic particles may cause the problems ofan increase in thickness of the adhesive layer at the same loadingamount and an increase in resistance between an electrode and theseparator. When the average particle diameter of the first adhesiveresin particles is less than 0.8 times the average particle diameter ofthe inorganic particle, the first adhesive resin particles mayinfiltrate to the porous coating layer, which may result in a failure information of an adhesive layer. In this case, since there may be littledifference in diameter between the first adhesive resin particles andthe second adhesive resin particles, the resistance of an electrode maybe significantly increased, like in the case of adhesive resin particleshaving a uniform size.

Meanwhile, when the average particle diameter of the second adhesiveresin particles as compared to the average particle diameter of theinorganic particles is within the above-defined range, the separatoritself may have low resistance, show significantly decreased incrementin resistance after lamination with an electrode, and may be providedwith excellent adhesion between the electrode and the separator.

Each of the first adhesive resin particle and the second adhesive resinparticle may independently include one or more selected from the groupconsisting of styrene butadiene rubber (SBR), acrylonitrile-butadienerubber, acrylonitrile-butadiene-styrene rubber, polybutylacrylate-co-ethylhexyl acrylate, polymethyl methacrylate-co-ethylhexylacrylate, polyacrylonitrile, polyvinyl chloride, polyvinylidenefluoride, polyvinyl alcohol, styrene and polycyanoacrylate.

According to an embodiment of the present disclosure, the inorganicparticles are not particularly limited, as long as they areelectrochemically stable. In other words, the inorganic particles arenot particularly limited, as long as they cause no oxidation and/orreduction in the operating voltage range (e.g. 0-5V based on Li/Li⁺) ofan applicable electrochemical device. Particularly, when using inorganicparticles having a high dielectric constant, they may contribute to anincrease in dissociation degree of the electrolyte salt, particularlylithium salt, in a liquid electrolyte, and thus can improve ionconductivity of the electrolyte.

For these reasons, the inorganic particles may include inorganicparticles having a dielectric constant of 5 or more, inorganic particlescapable of transporting lithium ions or a mixture thereof.

The inorganic particles having a dielectric constant of 5 or more mayinclude Al₂O₃, SiO₂, ZrO₂, AlO(OH), TiO₂, BaTiO₃, Pb(Zr_(x)Ti_(1-x))O₃(PZT, wherein 0<x<1), Pb_(1-x)La_(x)Zr_(1-y)Ti_(y)O₃ (PLZT, wherein0<x<1, 0<y<1), (1-x)Pb(Mg_(1/3)Nb_(2/3))O₃-x-PbTiO₃ (PMN-PT, wherein0<x<1), hafnia (HfO₂), SrTiO₃, SnO₂, CeO₂, MgO, NiO, CaO, ZnO, SiC orcombinations thereof.

Particular examples of the inorganic particles capable of transportinglithium ions include lithium phosphate (Li₃PO₄), lithium titaniumphosphate (Li_(x)Ti_(y)(PO₄)₃, 0<x<2, 0<y<3), lithium aluminum titaniumphosphate (Li_(x)Al_(y)Ti_(z)(PO₄)₃, 0<x<2, 0<y<1, 0<z<3),(LiAlTiP)_(x)O_(y)-based glass (0<x<4, 0<y<3), lithium lanthanumtitanate (Li_(x)La_(y)TiO₃, 0<x<2, 0<y<3), lithium germaniumthiophosphate (Li_(x)Ge_(y)P_(z)S_(w), 0<x<4, 0<y<1, 0<z<1, 0<w<5),lithium nitride (Li_(x)N_(y), 0<x<4, 0<y<2), SiS₂-based glass(Li_(x)Si_(y)S_(z), 0<x<3, 0<y<2, 0<z<4), P₂S₅-based glass(Li_(x)P_(y)S_(z), 0<x<3, 0<y<3, 0<z<7), or combinations thereof.

There is no particular limitation in average particle diameter of theinorganic particles. However, the inorganic particles preferably have anaverage particle diameter of 0.001-10 μm with a view to formation of aporous coating layer having a uniform thickness and adequate porosity.More preferably, the inorganic particles may have an average particlediameter of 100-700 nm, and more preferably an average particle diameterof 150-600 nm.

In the separator according to an embodiment of the present disclosure,the first adhesive resin particles may be present in an amount of 30-90wt %, preferably 50-85 wt %, based on the total weight of the firstadhesive resin particles and the second adhesive resin particles. Withinthe above-defined range of 30-90 wt %, resistance of an electrodeassembly may be maintained at a low level after lamination with anelectrode, and excellent adhesion may be provided between the electrodeand the separator.

The adhesive layer may have a thickness of 0.5-3 μm, or 0.5-2 μm. Withinthe above-defined range of 0.5-3 μm, it may be possible to improve theadhesion between the electrode and the separator while not increasingresistance significantly.

In the separator according to an embodiment of the present disclosure,the porous polymer substrate may be a porous polymer film substrate orporous polymer non-woven web substrate.

The porous polymer film substrate may include a porous polymer filmincluding a polyolefin, such as polyethylene or polypropylene. Forexample, such a polyolefin porous polymer film substrate may realize ashut-down function at a temperature of 80-130° C.

Herein, the polyolefin porous polymer film may include a polymer formedof polyethylene, such as high-density polyethylene, linear low-densitypolyethylene, low-density polyethylene and ultrahigh-molecular weightpolyethylene polypropylene, polybutylene and polypentene alone or incombination.

In addition, the porous polymer film substrate may be prepared by usingvarious polymers, such as polyesters, in addition to polyolefins andforming the polymers into a film shape. The porous polymer filmsubstrate may be formed to have a stacked structure of two or more filmlayers, wherein each film layer may include the abovementioned polymers,such as polyolefins and polyesters, alone or in combination.

In addition to the above-mentioned polyolefins, the porous polymer filmsubstrate and the porous non-woven web substrate may includepolyethylene terephthalate, polybutylene terephthalate, polyester,polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone,polyether sulfone, polyphenylene oxide, polyphenylene sulfide,polyethylene naphthalene, or the like, alone or in combination.

Although there is no particular limitation in the thickness of theporous polymer substrate, the porous polymer substrate may have athickness of 1-100 μm, particularly 5-50 μm. Although the pore size andporosity of the pores present in the porous polymer substrate are notalso limited particularly, it is preferred that the pore size andporosity are 0.01-50 μm and 10-95%, respectively.

In the separator according to an embodiment of the present disclosure,the binder polymer used for forming the porous coating layer may be oneused currently for forming a porous coating layer in the art.Particularly, a polymer having a glass transition temperature (T_(g)) of−200 to 200° C. may be used. This is because such a polymer can improvethe mechanical properties, such as flexibility and elasticity, of thefinally formed porous coating layer. Such a binder polymer may functionas a binder which connects and stably fixes the inorganic particles witheach other, and thus may contribute to prevention of degradation ofmechanical properties of a separator having a porous coating layer.

In addition, the binder polymer may have or may not have ionconductivity. When using a polymer having ion conductivity, it may bepossible to further improve the performance of an electrochemicaldevice. Therefore, a binder polymer having a dielectric constant as highas possible may be used. In fact, since the dissociation degree of asalt in an electrolyte depends on the dielectric constant of the solventfor the electrolyte, a binder polymer having a higher dielectricconstant can improve the salt dissociation degree in an electrolyte. Thebinder polymer may have a dielectric constant ranging from 1.0 to 100(measured at a frequency of 1 kHz), particularly 10 or more.

In addition to the above-mentioned function, the binder polymer may becharacterized in that it is gelled upon the impregnation with a liquidelectrolyte and thus show a high degree of swelling. Thus, the binderpolymer may have a solubility parameter (i.e., Hildebrand solubilityparameter) of 15-45 MPa^(1/2) or 15-25 MPa^(1/2) and 30-45 MPa^(1/2).Therefore, hydrophilic polymers having many polar groups may be usedmore frequently as compared to hydrophobic polymers, such aspolyolefins. When the solubility parameter is less than 15 MPa^(1/2) ormore than 45 MPa^(1/2), it may be difficult for the binder polymer to beswelled with a conventional liquid electrolyte for a battery.

Non-limiting examples of the binder polymer include but are not limitedto: polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidenefluoride-co-trichloro ethylene, polymethyl methacrylate, polyethylhexylacrylate, polybutyl acrylate, polyacrylonitrile, polyvinyl pyrrolidone,polyvinyl acetate, polybutyl acrylate-co-ethylhexyl acrylate,polyethylene-co-vinyl acetate, polyethylene oxide, polyarylate,cellulose acetate, cellulose acetate butyrate, cellulose acetatepropionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethyl sucrose, pullulan and carboxymethyl cellulose.

The weight ratio between the inorganic particles and the binder polymermay be 50:50-99:1, particularly 70:30-95:5. When the weight ratio of theinorganic particles based on the binder polymer satisfies theabove-defined range of 50:50-99:1, it may be possible to prevent theproblem of degradation of pore size and porosity of a coating layercaused by an increased amount of binder polymer. It may also be possibleto solve the problem of weakening of peeling resistance of a coatinglayer caused by an insufficient amount of binder polymer.

Besides the above-mentioned inorganic particles and polymer, theseparator according to an embodiment of the present disclosure mayfurther include other additives as ingredients for the porous coatinglayer.

Although there is no particular limitation in the thickness of theporous coating layer, the porous coating layer may have a thickness of1-10 μm, particularly 1.5-6 μm. Also, there is no particular limitationin the porosity of the porous coating layer, the porous coating layermay have a porosity of 35-65%.

The separator according to an embodiment of the present disclosure maybe obtained by methods generally known in the art. According to anembodiment of the present disclosure, a slurry for forming a porouscoating layer may be prepared by dispersing inorganic particles in apolymer dispersion containing a binder polymer dispersed in a solvent,and then the slurry for forming a porous coating layer may be applied toand dried on a porous polymer substrate to form a porous coating layer.Next, a slurry for forming an adhesive layer which includes the firstadhesive resin particles and the second adhesive resin particles havinga different size may be prepared, and then the slurry for forming anadhesive layer may be applied to and dried on the surface of the porouscoating layer to form an adhesive layer. The slurry for forming anadhesive layer may be applied preferably through a slot coating processor dip coating process.

In this case, it may be possible to reduce the resistance of theseparator by controlling the size of the first adhesive resin particlesand that of the second adhesive resin particles to a predeterminedratio. According to an embodiment of the present disclosure, the averageparticle diameter of the first adhesive resin particles may becontrolled to 0.8-3 times of the average particle diameter of theinorganic particles and the average particle diameter of the secondadhesive resin particles may be controlled to 0.2-0.6 times of theaverage particle diameter of the inorganic particles, thereby reducingthe resistance of the separator. In addition, it may be possible toincrease the adhesion between the separator and the electrode whilereducing the resistance of the separator by controlling the content ofthe first adhesive resin particles having a larger diameter to be largerthan the content of the second adhesive resin particles. Non-limitingexamples of the solvent that may be used herein include water, acetone,tetrahydrofuran, methylene chloride, chloroform, dimethylformamide,N-methyl-2-pyrrolidone, methyl ethyl ketone, cyclohexane or combinationsthereof. Preferably, the solvent may be water.

Although there is no particular limitation in the process for coatingthe slurry for forming a porous coating layer onto the porous polymersubstrate, it is preferred to use a slot coating or dip coating process.A slot coating process includes coating the slurry supplied through aslot die onto the whole surface of a substrate and is capable ofcontrolling the thickness of a coating layer depending on the fluxsupplied from a metering pump. In addition, dip coating includes dippinga substrate into a tank containing slurry to carry out coating and iscapable of controlling the thickness of a coating layer depending on theconcentration of the slurry and the rate of removing the substrate fromthe slurry tank. Further, in order to control the coating thickness moreprecisely, it is possible to carry out post-metering through a Mayer baror the like, after dipping.

Then, the porous substrate coated with the slurry for forming a porouscoating layer may be dried by using a dryer, such as an oven, therebyforming a porous coating layer on at least one surface of the porouspolymer substrate.

In the porous coating layer, the inorganic particles may be bound amongthemselves by the binder polymer while they are packed and are incontact with each other. Thus, interstitial volumes are formed among theinorganic particles and the interstitial volumes become vacant spaces toform pores.

In other words, the binder polymer attaches the inorganic particles toeach other so that they may retain their binding states. For example,the binder polymer connects and fixes the inorganic particles with eachother. In addition, the pores of the porous coating layer may be thoseformed by the interstitial volumes among the inorganic particles whichbecome vacant spaces. The space is defined by the inorganic particlesfacing each other substantially in a closely packed or densely packedstructure of the inorganic particles.

The electrochemical device according to another aspect of the presentdisclosure includes a cathode, an anode and a separator interposedbetween the cathode and the anode, wherein the separator is theabove-described separator according to an embodiment of the presentdisclosure.

The electrochemical device includes any device which carries outelectrochemical reaction, and particular examples thereof include alltypes of primary batteries, secondary batteries, fuel cells, solar cellsor capacitors such as super capacitor devices. Particularly, among thesecondary batteries, lithium secondary batteries, including lithiummetal secondary batteries, lithium ion secondary batteries, lithiumpolymer secondary batteries or lithium ion polymer ion batteries, arepreferred.

The two electrodes, cathode and anode, used in combination with theseparator according to the present disclosure are not particularlylimited, and may be obtained by allowing electrode active materials tobe bound to an electrode current collector through a method generallyknown in the art. Among the electrode active materials, non-limitingexamples of a cathode active material include conventional cathodeactive materials that may be used for the cathodes for conventionalelectrochemical devices. Particularly, lithium manganese oxides, lithiumcobalt oxides, lithium nickel oxides, lithium iron oxides or lithiumcomposite oxides containing a combination thereof are preferably used.Non-limiting examples of an anode active material include conventionalanode active materials that may be used for the anodes for conventionalelectrochemical devices. Particularly, lithium-intercalating materials,such as lithium metal or lithium alloys, carbon, petroleum coke,activated carbon, graphite or other carbonaceous materials are usedpreferably. Non-limiting examples of a cathode current collector includefoil made of aluminum, nickel or a combination thereof. Non-limitingexamples of an anode current collector include foil made of copper,gold, nickel, nickel alloys or a combination thereof.

The electrolyte that may be used in the electrochemical device accordingto the present disclosure is a salt having a structure of A⁺B⁻, whereinA⁺ includes an alkali metal cation such as Li⁺, Na⁺, K⁺ or a combinationthereof and B⁻ includes an anion such as PF₆ ⁻, BF₄ ⁻, Cl⁻, Br⁻, I⁻,ClO₄ ⁻, AsF₆ ⁻, CH₃CO₂ ⁻, CF₃SO₃ ⁻, N(CF₃SO₂)₂ ⁻, C(CF₂SO₂)₃ ⁻ or acombination thereof, the salt being dissolved or dissociated in anorganic solvent including propylene carbonate (PC), ethylene carbonate(EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropylcarbonate (DPC), dimethyl sulfoxide, acetonitrile, dimethoxyethane,diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), ethylmethyl carbonate (EMC), gamma-butyrolactone (g-butyrolactone) or acombination thereof. However, the present disclosure is not limitedthereto.

Injection of the electrolyte may be carried out during the process formanufacturing a battery depending on the manufacturing process of afinal product and properties required for a final product. In otherwords, injection of the electrolyte may be carried out, for instance,before the assemblage of a battery or in the final step of theassemblage of a battery.

Examples will be described more fully hereinafter so that the presentdisclosure can be understood with ease. The following examples may,however, be embodied in many different forms and should not be construedas limited to the exemplary embodiments set forth therein. Rather, theseexemplary embodiments are provided so that the present disclosure willbe thorough and complete, and will fully convey the scope of the presentdisclosure to those skilled in the art.

EXAMPLE 1 1) Manufacture of Anode

Artificial graphite as an anode active material, carbon black as aconductive material, carboxymethyl cellulose (CMC) as a dispersing agentand polyvinylidene fluoride (PVDF) as a binder were mixed with water ata weight ratio of 95.8:1:1.2:2 to obtain an anode slurry. The anodeslurry was coated onto copper (Cu) foil to a thickness of 50 μm to forma thin electrode plate, which, in turn, was dried at 135° C. for 3 hoursand pressed to obtain an anode.

2) Manufacture of Cathode

LiCoO₂ as a cathode active material, carbon black as a conductivematerial and polyvinylidene fluoride (PVDF) as a binder were introducedto N-methyl-2-pyrrolidone (NMP) at a weight ratio of 96:2:2 and thenmixed to obtain a cathode slurry. The resultant cathode slurry wascoated onto aluminum foil (thickness 20 μm) as a cathode currentcollector to a capacity of 3.1 mAh/cm² to obtain a cathode.

3) Manufacture of Separator 3-1) Formation of Porous Coating Layer

Carboxymethyl cellulose (CMC) was dissolved in water at room temperatureto create a binder polymer solution, and Al₂O₃ inorganic particles(Sumitomo Co., AES11, particle size 500 nm) were introduced to thebinder polymer solution, followed by agitation, to prepare ahomogeneously dispersed slurry. Herein, the inorganic particles and CMCwere used at a weight ratio of 95:5. Next, an acrylic binder, polybutylacrylate-co-ethylhexyl acrylate (Toyo chem., CSB130), as a binderpolymer was introduced to the dispersed slurry to obtain a slurry for aporous coating layer. Herein, CMC and the acrylic binder were used at aweight ratio of 98:5. The slurry for a porous coating layer was appliedto one surface of a polyethylene porous polymer substrate (Asahi Co.,ND509) by using a doctor blade and dried at 60° C. for 1 minute toprepare a porous polymer substrate having a porous coating layer formedthereon. The porous coating layer had a thickness of 2 μm.

3-2) Coating of Adhesive Layer

A slurry for forming an adhesive layer was applied to the surface of theporous coating layer formed on the porous polymer substrate obtained asdescribed above, followed by drying at 60° C. for 1 minute, to form anadhesive layer. The adhesive layer was prepared as follows. At roomtemperature, polymethyl methacrylate-co-ethylhexyl acrylate (Zeon Co.,LP17, particle size 500 nm) as the first adhesive resin particles andpolybutyl acrylate-co-ethylhexyl acrylate (Toyochem. Co., CSB130,particle size 150 nm) as the second adhesive resin particles weredispersed homogeneously in water to prepare a slurry for forming anadhesive layer. The first adhesive resin particles and the secondadhesive resin particles were used at a weight ratio of 85:15.

The slurry for forming an adhesive layer was applied to the porouscoating layer obtained from 3-1) in an amount of 1.0 g/m² and then driedat 60° C. for 1 minute to form an adhesive layer on the surface of theporous coating layer. The ratio of the diameter of the second adhesiveresin particles to that of the first adhesive resin particles was 0.3,and the adhesive layer had a thickness of 1 μm.

4) Adhesion Between Separator and Electrode

Then, the separator was laminated with the anode so that the adhesivelayer faced the anode active material layer of the anode as described in1), and then pressing was carried out at 90° C. under 8.5 Mpa for 1second to obtain an electrode assembly including the anode laminatedwith the separator.

EXAMPLES 2-4

Separators were obtained in the same manner as described in Example 1,except that the average particle diameter of the inorganic particles,the first adhesive resin particles and the second adhesive resinparticles, and content of the first adhesive resin particles and thesecond adhesive resin particles were controlled as shown in thefollowing Table 1.

TABLE 1 Example 1 Example 2 Particle Particle Example 3 Example 4diameter of the diameter of the Content of the Content of the firstadhesive first adhesive first adhesive first adhesive resin particlesresin particles resin particles resin particles and that of the and thatof the and that of the and that of the second adhesive second adhesivesecond adhesive second adhesive resin particles resin particles resinparticles resin particles Particle diameter 500 nm 500 nm 500 nm 500 nmof the first adhesive resin particles Particle diameter 150 nm 150 nm150 nm 150 nm of the second adhesive resin particles Particle diameter500 nm 250 nm 500 nm 500 nm of inorganic particles Particle diameter 1    2    1    1   of the first adhesive resin particles to that ofinorganic particles Particle diameter 0.3 0.6 0.3 0.3 of the secondadhesive resin particles to that of inorganic particles Particlediameter 3   3   3   3   of the first adhesive resin particles to thatof the second adhesive resin particles Content of the 85:15 85:15 50:5070:30 first adhesive resin particles to that of the second adhesiveresin particles (weight ratio) Resistance of  0.90  0.83  0.82  0.86separator (Ω) Resistance after  1.91  1.73  1.83  1.88 lamination withelectrode (Ω) Adhesion between 40   54   35   37   electrode andseparator (gf/15 mm)

Comparative Example 1

A separator was obtained in the same manner as described in Example 1,except that only the first adhesive resin particles were used in theslurry for forming the adhesive layer.

Comparative Example 2

A separator was obtained in the same manner as described in Example 1,except that only the second adhesive resin particles were used in theslurry for forming the adhesive layer.

Comparative Examples 3-7

Separators were obtained in the same manner as described in Example 1,except that the average particle diameter of the inorganic particles,the first adhesive resin particles and the second adhesive resinparticles, and content of the first adhesive resin particles and thesecond adhesive resin particles were controlled as shown in thefollowing Table 2.

TABLE 2 Comp. Ex. Comp. Ex. Comp. Ex. Comp. Ex. Comp. Ex. 1 2 3 4 Comp.Ex. Comp. Ex. 7 Particle Particle Particle Particle 5 6 Particlediameter diameter diameter diameter Content of Content of diameter ofthe first of the first of the first of the first the first the first ofthe first adhesive adhesive adhesive adhesive adhesive adhesive adhesiveresin resin resin resin resin resin resin particles particles particlesparticles particles particles particles and that of and that of and thatof and that of and that of and that of and that of the second the secondthe second the second the second the second the second adhesive adhesiveadhesive adhesive adhesive adhesive adhesive resin resin resin resinresin resin resin particles particles particles particles particlesparticles particles Particle 500 nm — 500 nm 500 nm 500 nm 500 nm 1000nm  diameter of the first adhesive resin particles Particle — 150 nm  90nm 350 nm 150 nm 150 nm 150 nm diameter of the second adhesive resinparticles Particle 500 nm 500 nm 500 nm 500 nm 500 nm 500 nm 250 nmdiameter of inorganic particles Particle 1 — 1 1 1 1 4 diameter of thefirst adhesive resin particles to that of inorganic particles Particle —0.3 0.18 0.7 0.3 0.3 0.6 diameter of the second adhesive resin particlesto that of inorganic particles Particle — — 5.5 1.4 3 3 6.7 diameter ofthe first adhesive resin particles to that of the second adhesive resinparticles Content of 100:0 0:100 85:15 85:15 20:80 95:5 85:15 the firstadhesive resin particles tot hat of the second adhesive resin particles(weight ratio) Resistance 0.93 1.01 0.88 0.90 0.98 1.03 Hard to ofseparator prepare (Ω) adhesive Resistance 4.27 1.00 4.02 4.13 3.52 3.93resin of after 1000 nm lamination or more with electrode (Ω) Adhesion 301 25 28 7 27 between electrode and separator (gf/15 mm)

Test Methods 1) Determination of Particle Diameter

The average particle diameter of the inorganic particles, the firstadhesive resin particles and the second adhesive resin particles weredetermined by using the laser diffraction method (Microtrac MT 3000).

2) Determination of Separator Resistance

The resistance means a resistance value when a separator is impregnatedwith an electrolyte. It was determined through impedance analysis byusing an electrolyte containing 1M LiBF₄ in propylene carbonate/ethylenecarbonate (weight ratio 1:1) at 20° C.

3) Determination of Resistance after Lamination with Electrode

The resistance means a resistance value when an electrode assembly isimpregnated with an electrolyte. It was determined through impedanceanalysis by using an electrolyte containing 1M LiBF₄ in propylenecarbonate/ethylene carbonate (weight ratio 1:1) at 20° C.

4) Determination of Adhesion (Lami Strength) between Electrode andSeparator

An anode was obtained in the same manner as Example 1-1) and cut into asize of 15 mm×100 mm. Each of the separators according to Examples 1-4and Comparative Examples 1-7 was cut into a size of 15 mm×100 mm. Eachseparator was stacked with a corresponding anode, inserted between PETfilms (100 μm) and adhered with each other by using a flat press.Herein, the flat press procedure was carried out by heating at 90° C.under 8.5 MPa for 1 second. The end of the adhered separator and anodewas then mounted to an UTM system (LLOYD Instrument LF Plus), and thenthe force required for separating the separator from the anode facingthe separator was measured by applying force thereto at 180° with a rateof 300 mm/min.

Description Of Drawing Numerals

-   100: Separator-   10: Porous polymer substrate-   20: Porous coating layer-   21: Inorganic particles-   30: Adhesive layer-   31: First adhesive resin particles-   32: Second adhesive resin particles

What is claimed is:
 1. A separator for an electrochemical device whichcomprises: a porous polymer substrate having pores; a porous coatinglayer present on at least one surface of the porous polymer substrate,and comprising inorganic particles and a binder polymer disposedpartially or totally on a surface of the inorganic particles, whereinthe binder polymer connects and fixes the inorganic particles with eachother; and an adhesive layer present on a surface of the porous coatinglayer, and comprising first adhesive resin particles having an averageparticle diameter corresponding to 0.8-3 times of an average particlediameter of the inorganic particles and second adhesive resin particleshaving an average particle diameter corresponding to 0.2-0.6 times ofthe average particle diameter of the inorganic particles, wherein thefirst adhesive resin particles are present in an amount of 30-90 wt %based on a total weight of the first adhesive resin particles and thesecond adhesive resin particles.
 2. The separator for an electrochemicaldevice according to claim 1, wherein the average particle diameter ofthe inorganic particles is 100-700 nm.
 3. The separator for anelectrochemical device according to claim 1, wherein the first andsecond adhesive resin particles independently comprise one or more resinselected from the group consisting of styrene butadiene rubber (SBR),acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber,polybutyl acrylate-co-ethylhexyl acrylate, polymethylmethacrylate-co-ethylhexyl acrylate, polyacrylonitrile, polyvinylchloride, polyvinylidene fluoride, polyvinyl alcohol, styrene andpolycyanoacrylate.
 4. The separator for an electrochemical deviceaccording to claim 1, wherein the average particle diameter of the firstadhesive resin particles is 1-2.5 times of the average particle diameterof the inorganic particles, and the average particle diameter of thesecond adhesive resin particles is 0.3-0.6 times of that the averageparticle diameter of the inorganic particles.
 5. The separator for anelectrochemical device according to claim 1, wherein the averageparticle diameter of the first adhesive resin particles is 1-2 times ofthe average particle diameter of the inorganic particles, and theaverage particle diameter of the second adhesive resin particles is0.3-0.6 times of the average particle diameter of the inorganicparticles.
 6. The separator for an electrochemical device according toclaim 1, wherein the first adhesive resin particles are present in anamount of 50-85 wt % based on the total weight of the first adhesiveresin particles and the second adhesive resin particles.
 7. Theseparator for an electrochemical device according to claim 1, whereinthe inorganic particles comprise one or more selected from the groupconsisting of BaTiO₃, Pb(Zr_(x)Ti_(1-x))O₃ (PZT, 0<x<1),Pb_(1-x)La_(x)Zr_(1-y)Ti_(y)O₃ (PLZT, 0<x<1, 0<y<1),(1-x)Pb(Mg_(1/3)Nb_(2/3))O₃ ⁻xPbTiO3 (PMN-PT, 0<x<1), hafnia (HfO₂),SrTiO₃, SnO₂, CeO₂, MgO, NiO, CaO, ZnO, ZrO₂, Y₂O₃, Al₂O₃, AlO(OH),SiO₂, TiO₂ and SiC.
 8. The separator for an electrochemical deviceaccording to claim 1, wherein the porous coating layer has a thicknessof 1-10 μm.
 9. The separator for an electrochemical device according toclaim 1, wherein the adhesive layer has a thickness of 0.5-3 μm.
 10. Theseparator for an electrochemical device according to claim 1, whereinthe porous coating layer is present directly on the surface of theporous polymer substrate.
 11. The separator for an electrochemicaldevice according to claim 1, wherein the adhesive layer is presentdirectly on the surface of the porous coating layer.
 12. The separatorfor an electrochemical device according to claim 1, wherein the firstand second adhesive resin particles comprise the same resin.
 13. Theseparator for an electrochemical device according to claim 1, whereinthe first and second adhesive resin particles comprise different resins.14. The separator for an electrochemical device according to claim 1,wherein an upper portion of the adhesive layer has a larger number ofpores as compared to a lower portion of the adhesive layer, said lowerportion being in contact with the surface of the porous coating layer.15. An electrochemical device comprising a cathode, an anode and aseparator interposed between the cathode and the anode, wherein theseparator is defined in claim
 1. 16. The electrochemical deviceaccording to claim 15, which is a lithium secondary battery.